Alkali metal salt-organic sulfoxt



Patented Nov. 20, 1951 DETERGENT COMPO SITIONS AGAINSTDETERIIORATION 0F VITREOUS- AND CERAMIC-WARE SURFACES Leslie R. Bacon, "Wyandotte, and Joseph 1V.

Otrhalek, Detroit, Mich, assignors to Wfyan dotte Chemicals Corporation,wyandottefiMich a corporation of Michigan NotDi'a'win'g. Application January I3, 1936, Serial No. 138,518

It has previously been ascertained that -highly alkaline solutions, containing free caustic alkali, such as NaOH, can be inhibited against alkali attack of vitreous and ceramic surfaces (such attack efiecting actualdissolution of the vitreous or ceramic material accompanied b'ya scratched, scuffed, etched or worn appearance of the sur face thereof) by the addition of a water-soluble zinc compound (Wegst, Bacon, andVaughn U. S.

Pat. No. 2,447,297), a water-soluble beryllium compound (Wegst, Bacon, and Vaughn, U. 8'. Pat. No. 2,419,805) or a water-soluble aluminum compound (Cooper, U. S."Pat. No. 2,241,984), We have now discovered that even mildly alkaline detergent and washing compositions have-a corrosive or deteriorative efiect .on vitreous and ceramic surfaces. "That is to say, the alkali metal salts which are employed as builders for soap and synthetic detergents in compositions ,ror washing glassware and-dishes (such aslaboratory glassware, overglaze decorated chinawa're and earthenware), themselves possess .the ability to attack glass and ceramic ware, even though their alkalinity in aqueous solutions may .be on the order ofI8-1O pH as compared .tothe greater than 12 pH alkalinity of solutions containing free caustic alkali.

The problem of compounding alkali metal salts, such as sodium-carbonates, -phosphates, -silicates and-sulfates, witha water-soluble Zn-, Beor Al-compound, however, was found to be extremely difiicult because such chemical compounds when brought together in aqueous solutions, were found to be incompatible. 'That'isto say, it was found as ,a general rule, that the alkali metal builder salts when combined with the inhibitingcompounds such astsodium zincate, zinc sulfate, beryllium sulfate, sodium aluminate and aluminum sulfate, produced aqueous solutions which either contained a precipitate or had a turbid or cloudy appearance. It is quite ,possible that the excess of free caustic alkali .as present in the inhibited washing compounds of the above-mentioned II. S. Pats. Nos. 2,449,805 and 2,447,297 wherein it is disclosed that up to 40% of alkali metal carbonates, -phosphates and -silicates may be present, exerted a ,powerful solubilizing effect on the precipitate or turbidityforming product which would otherwise result from the presence of the alkali metal :salt and the inhibiting compound. Thus, the problem of compounding a washing composition based on an alkali metal'salt'or-salts, a syntheticdetergent selected from the group consisting of the sodium salts of alkyl sulfonates, alkyl sulfates and alkyl- 7 I listed, are commercially available products arylsulfohates whose alkyl group contains -l-0=-1"8' carbon atoms and a Zn'-, -l3eor Al-inhibitinfg compound involved only the discovery of those'particularingredientSWhich WOuRl-be patible with each other, but also their proper balance and determination of the effective amount of inhibiting compound which should be present in order to overcome thexJQOlSIQSLVB and, deterioratiye action lglassrand ;.ceramic faces.

Summary of invention Our invention therefore resides mine cry of the following range pfopoiti'oh's of in gredients which are capable of prdduingaiileaii," non-turbid and precipitate-free"solution when; dissolved in water at customary workingicon"- ingredients t Bnefexfzed Ran .Operable .Range total alkalinity as N820 0'13 -Z43% Materials standard specification, AST-M desiguation:.DA,57:39. V

i A mixture of sodium caigiouateand sodium bicarbonate having ,a

The synthetic detergent compounds. :as above precisely identified as group is derived from a petroleum hydrocarbon and contains 10-18 carbon atoms.

Such com- -pound's are synthesizedaccording tp:theprocesses is-gn 2,220,099. They are commercially available under the product names Kreelon, Nacconol, Santomerse and Oronite.

Sodium lauryl sulfate is the sodium salt of sulfated fatty alcohols such as are derived from coconut oil. This compound may be synthesized according to the process as disclosed in U. S. Pat. No. 1,968,79? and is commercially available under the product names of Duponol ME and Dreft.

Sodium alkyl sulfonate is derived from petroleum hydrocarbons or synthetic hydrocarbons, the alkyl group containing -16 carbon atoms. It is made by a process such as disclosed in U. S. Pat. No. 2,197,800. A commercially available form is sold under the product name M. P. 189.

Such compounds are usually commercially available and customarily used in their saltbuil form, i. e. containing a certain percentage of active agent. and the balance usualiy being the inorganic salt, Na2SO4. In the compositions of our invention, such synthetic detergents are present in their at least 35% active agent form. The water-soluble Zn-, Beor Alsalts are preferably derived from the following commercially available forms:

Sodium zincate ZnO-NaOH-HzO reaction product made according to U. S. Pat. No. 2,403,157

Sodium aluminate A12(SO4)3.18H2O BeSO4.4H2O v Beryl-NaOH reaction product made according to U. S. Pat. No. 2,474,392 or Example 2 of U. S. Pat. No. 2,419,805.

Solution compatibility In our efiorts to discover a possible combination or combinations of alkali metal salts and Zn-, Beand Alcompounds which might possiblysolve the problem of producing a clear and compatible aqueous solution, preliminary formulations were made up consisting of 90% by weight of several different sodium carbonates,

Although the foregoing test results did not seem to be too promising, they did give the clue that possibly, by a proper balance of those sodium carbonates and sodium phosphates which, individually at least, showed compatibility with an inhibitor compound, then by combination and adjustment of ingredients, proper compatibility in aqueous solution might be achieved. At the same time that the question of possible compatibility of the ingredients NaHCOz, modified soda, NazCOs, NasPaOio, NasP4O13, (NaPOfis, and inhibitor compounds were being investigated, several different types of synthetic organic detergents and surface active agents, including anionic-, non-ionicand cationic types, were included in the formulations. Of these synthetic detergents, it was found that those anionic compounds selected from the group consisting of the sodium salts of alkyl sulfonates, alkyl sulfates and alkylarylsulfonates whose alkyl group contains 10-18 carbon atoms were the most suitable. It was thereby found that when the following specified ingredients were maintained in the range proportions as tabulated below, that clear, compatible aqueous solutions were produced:

Per Cent Ingredient by weight Sodium Carbonate: NaHC Modifiedsoda 20-30 N320 0': Sodium Phosphate:

N sPaO In further explanation of our invention, the following exemplary formulations are given as being preferred and well adapted for commercial use.

-silicates, -phosphates, -borate compounds and EXAMPLE 1 10% of inhibiting compound In the case of the BeSOrAHzO inhibitor compound, this propor- In edients Per Cent tion was changed to 99.7% alkaline sodium salt gr eight and 0.3% inhibitor. Such prepared formulations were then dissolved in distilled water at g g gs g g egg ggg (40% mive 3g 0 um 103i 0B3 e 3 p F- m an amount C SDO d g o Sodium tripolyphosphate (NagPgOm) 22 by weight solids content; The resultant solu- ZmcsulfatMZnSOflmO) 6 tions, by visual observation, possessed the foll A sodium al larylsulfonate whose "keryl" or alkyl group 13 del lowing noted properties: rived from a pet r leum hydrocarbon and contains 11-16 carbon atoms.

TABLE I Inhibitor Omani Alkaline Salt ZnSOi(7H:O) NaoH-zno-mm n solumo) Beryl-NaOH NE2A1204 Alz(S04)s(18H:0)

-P- r P c P P P P P o P P P -P P P o P P P P P 'r P P P P P '1 P P P P P o P P P -P P P P P o P c P P P o P P o P P 0 P ,P 0 P o NalBiorlflHgou'u- P P P o P P Key: P=preclpitate. T=turbid or cloudy solution. O=no precipitate, clear solution (1. 9., compatible).

1 Product of U. 8. Pat. No. 2,403,157, 30% Z content.

5 This formulation, when dissolved in distilled water and other waters ofvarying; degrees of hardness, at a temperature of 120-130 F. and at a practical working solution of 0.6 by weight total solids basis, produced clear solutions con-- taining no precipitate, cloudiness or turbidity. When the amount of ZnSO4.7I-l2O was varied between 5 and 10%, at the expense of the sodium kerylbenzenesulfonate-NazSO-4 present, the solution clarity or compatibility was still maintained. However, on increasing the ZnSO-rflHzO content to 12%, there resulted a turbid solution having a little less than 0.5% by volume of precipitate in a standard ten grain hardness water. Thus, it was established that the tolerance of this formulation for more than 1'0 of inhibitor compound was quite critical.

EXAMPLE 2 Ingredients gkg g Sodium kerylbenzenesulfonate. (40% active agent) '55 Sodium bicarbonate (NaHCOa) g 25 Sodium tripolypliosphate (N85P3010) 1'5 NaOH-ZnO-Hfi reaction product (30% Z110 content). 5

Here again, it was discovered that the tolerance of the formulation for they water-soluble zinc compound was a maximum of 10%.

EXAMPLE 3 In 61 t PerbCent gre' en s 3" Weight Sodium kerylbenzenesulfonate (40% active agent) 55 Sodium bicarbonate NaH'O a) 25 Sodium tripolyphosp ate '(NarPaOw) 15 Beryllium sulfate (BeSOuiHzO) EXAMPLE 4 Per Cent Ingedients by Weight Sodium"kerylbenzeuesulfonate (40% activc'agent') Modified soda Sodium tripolyphosphate (Na5PaO1u) Beryllium sulfate (BeSO4;4HzO) The formulation of Example 5 likewise confirmed the maximum tolerance for the aluminum sulfate inhibitor compound. When the amount of inhibitor compound was increased from 4 to 6%, at the expense of the sodium kerylbenzenesulfonate-NazsOi present, a very excellent composition was obtained which displayed universal solution clarity in distilled, hard and soft waters, at a concentration of 0.6% solids basis and at temperatures of -130 F.

Corrosion inhibiting properties Formulations coming within the scope of our invention were subjected to an accelerated glass corrosion test described as follows:

Glass test tubes of a 10 x '75 mm. size, made from a borosilicate type glass, were first washed in a weak solution of sodium kerylbenzenesulfonate (60% Na2SO4 content) in distilled water and then thoroughly rinsed in distilled water. The. test tubes were then baked for 4 hours at 210 'F. to drive off all surface moisture, cooled and weighed.

Test detergent formulation solutions, according to those given in Examples l-5 inc. above, were then made up at a concentration of 0.6% total solids basis in either distilled water and/or tap water of 6 grains per gallon total hardness as CaCOa and placed in one liter capacity stainless steel beakers, the temperature of such solutions being maintained at 209:2" F.

Three of the previously prepared test tubes were then placed at random on the bottom of the so-prepared test solutions and permitted to remain there for a period of 13 hours, the temperature being maintained. Thereafter, the test tubes were removed from the test solutions, brushed free of any surface deposits with a soft test tube brush, rinsed with distilled water and baked as before to drive off surface moisture, then cooled and weighed to the nearest 0.2 mg. The average weight loss of the three specimen The above results are to be compared with control tests wherein the same formulations as in the above examples, but with no inhibitor :compound present were used to make up the detergent test solutions. In such control tests, the weight losses ranged from approximately 7-14- mgs. per tube in distilled water, and 4-! mgs. per tube in tap water.

Next, in order to determine the effective range content of inhibitor compound in the formulations of Examples 1-5, additional test formulations were made up wherein the amount of -inhibitor was varied over the. range of 040%, at the expense of the sodium kerylbenzenesulfonate- Na2SO4 present. The test solutions were made up at concentrations of 0.6% in both distilled water and tap water except in the case of the base formulation of Example 4 where distilled water only, and of Example 5 where tap water only, were used. In general, it was noted that distilled water solutions were more corrosive than tap water solutions. Hence the former presented the more severe test conditions. The results are given in the following Table III:

TABLE 111 Weight Loss Amount of Inhibitor (15/ tube) Base Formulation Present (ler Cent by welght) Distilled Tap Water Water Example 1 ZnSOnTHaO:

l) 14.3 7. 3 4. 8 3. l 2. 7 0.7 Example 2 9. 2 3. 8 7. 3 4. 4 5. 8 1.3 4. 4 0.0 0.3 Example 3 6. 7 3. 8 4. 8 0.8 4. 2 0.0 l. 7 0. 4 I 0.3 Example 4 6. 3 5. 2 2. l 1. 0.0 0. 0 Example 5 EXAMPLE 6 Per Cent Ingredients by Weight Sodium kerylbenzenesulionate (40% active agent) Sodium bicarbonate (N aHO 0;) Sodium tetraphosphatc (N 361 40 13) Aluminum sulfate (AIKSOOSJAHiO).

The above composition gave a clear solution in tap water of approximately 6 grain'hardness with no precipitate and gave no precipitate in grain hardness water. Such solutions were prepared at 0.3% concentration at 110-120 F. In the accelerated glass corrosion tests, this composition produced a weight loss of 0.4 mg. per tube, in distilled water.

EXAMPLE 7 Hexametaphosphate was substituted for the sodium tetraphosphate for the formulation of Example 6 with identical results in respect to solution clarity and absence of precipitate. The accelerated glass corrosion test results were slightly better however giving no weight loss in distilled water.

EXAMPLE 8 Per Cent Ingredients by Weight Sodium kerylbenzenesulionate (70% active agent) 51 Sodium bicarbonate (NaHCOa) 23 Sodium tripolyphosphate (Na5P301o)- 22 Aluminum sulfate (Al2(SO4)a.l4H2O). 4

The composition of this example made a clear solution of 0.3% concentration in tap water of approximately 6 grains per gallon total hardness and produced no precipitate in such tap water or in water of 15 grain hardness. The accelerated glass corrosion test showed a weight loss of 0.9 mg. per tube, in distilled water.

EXAMPLE 9 Sodium lauryl sulfate (85% active agent) was substituted for the sodium kerylbenzenesulfonate ingredient of Example 5. Identical clarity and lack of precipitate, as obtained in Example 8 was produced. The accelerated glass corrosion test showed a weight loss of 0.5 mg. per tube, in distilled water.

EXAMPLE 10 Sodium alkyl sulfonate active agent basis) whose alkyl group contained an average of 15 carbon atoms and was derived from a pctroleum hydrocarbon, as disclosed in U. S. Pat. No. 2,197,800, was substituted for the sodium kerylbenzenesulfonate of Example 5. Similar re- 7 suits were obtained as in Example 9.

- trol of glass and ceramic ware deterioration by alkaline salts. In such a range of concentration, by a further series of tests carried out on washing glass test tubes, and in the same manner as previously described, but wherein the concentration of the compositions of Examples 1, 2

ments, were immersed in 0.3% solutions of the.

and 5 were varied from 0.075% to above 2.0%, it was found that only 0.0-1.0 mg./tube weight loss was obtained in the range of 03-10% conchinaware and earthenware. Ornamental effects on such ware in the form of gold striping and banding is particularly sensitive to such action. Thus, for example, two difierent brands or types of overglaze chinaware dinner plates, containing gold striping as well as other colored pigcompositions of Examples 1 and 5 for periods of 13 hours and 36 hours and at a constant temperature of F. An uninhibited detergent composition consisting of sodium carbonate, -bi- It has also been found that the compositions of our invention are effective to inhibit deprecia-- tion of large, vitreous enamel-lined steel tanks.

It will be noted in the foregoing examples and descriptive matter that the percentage amounts of inhibitor compounds are given in terms of their actual solid weights and including com-- bined water of hydration or of constitution. However, in order to translate such stated proportions to a more empirical basis, the following conversion table gives the Zn-, Beand Almetallic oxide equivalent content or the several inhibitor compounds herein mentioned, vizz Thus, converting the 3-10% range proportion of inhibitor compounds to their metallic oxide content equivalent bases, it is seen that the corresponding minimum and maximum limits of water-soluble zinc compound are 0.85-5.66%-Zn content; of beryllium compound, .009-1.41% BeO content; and of aluminum compound, 0.474522% A1203 content. In the preferred 4-6% actual solid weight range of inhibitor compounds, the corresponding conversion limits are: zinc compound, 1.13-3.40% ZnO content; beryllium compound, .012-0.84% BeO content; and aluminum compound, 0.61-3.73% A1203 content.

As used in the specification and the appended claims the phrase NaOH, ZnO and H20 refers to the product made by the method of U. S. Patent No. 2,403,157. Similarly the phrase Be0Na0I-IH20 and fberyl-NaOH refers to the product made by the method of U. 5. Patent No. 2,474,392 or Example 2 of U. S. Patent No. 2,419,805.

Other modes of applying the principle of our invention may be employed, changes being made as regards to the details described, provided the features stated in any of the following claims or the equivalent of such be employed.

We, therefore, particularly point out and distinctly claim as our invention:

1. A detergent composition inhibited against deteriorative action on vitreous and ceramic surfaces, consisting essentially of 20-30% by weight of a carbonate selected from the group consisting of sodium bicarbonate, modified soda and sodium carbonate, -40% of a phosphate selected from the group consisting of sodium tripolyphosphate, sodium tetraphosphate and sodium hexametaphosphate, 40-70% of a synthetic detergent selected from the group consisting of the sodium salts of alkyl sulfonates, alkyl sulfates and alkylarylsulfonates, wherein the alkyl group contains 10-18 carbon atoms, said synthetic detergent being present in at least 35% active agent form; and 3-10% of an inhibitor compound selected from the group consisting of the zincates, berylliates and aluminates of sodium and the sulfates of zinc, beryllium and aluminum compounds and corresponding to a 0.85-5.66% ZnO equivalent weight, a .009-1.41% Be0 equivalent weight, and a 0.47-6.22% A1203 equivalent weight, respectively.

2. The composition as in claim 1 wherein the inhibitor compound is zinc sulfate.

3. The composition as in claim 1 wherein the inhibitor compound is the reaction product of NaOH, ZnO and H20 of 30% Zn0 content.

4. The composition as in claim 1 wherein the inhibitor compound is aluminum sulfate.

5. A detergent composition inh it d against 10 deteriorative action on vitreous and ceramic Surfaces, consisting essentially of 23-25% by weight of a carbonate selected from the group consisting of sodium bicarbonate, modified soda and sodium carbonate, 15-22% of a'phosphate selected from the group consisting of sodium tripolyphosphate, sodium tetraphosphate and sodium hexameta phosphate, 49-55% of a synthetic detergent selected from the group consisting of the sodium salts of alkyl sulfonates, alkyl sulfates and alkylary-lsulfonates, wherein the alkyl group contains IO-18 carbon atoms, said synthetic detergent being present in at least 35% active agent form; and 4-6% of an inhibitor compound selected from'the group consisting'of the zincates, beryllia-tes and aluminates of sodium and the sulfates of zinc, beryllium. and aluminum compounds and corresponding to a 1.13-3.40% 'zno equivalent weight, a BIZ-0.84% BeO content, and. a 0.61-3.73% A1203 equivalent weight, respectively.

6. The composition as in claim 5 wherein the inhibitor compound is zinc sulfate.

7. The composition as in claim 5 wherein the inhibitor compound is the reaction product of NaOH, ZnO and H20 of 30% Zn0 content.

8. The composition as in claim 5 wherein the inhibitor compound i aluminum sulfate,

9. A detergent composition inhibited against deteriorative action on vitreous and ceramic surfaces, consisting essentially of 20-30% by weight of a carbonate selected nom the group consisting of sodium bicarbonate and modified soda, 10-40%- of sodium tripolyphosphate, 40-70% of sodium kerylbenzenesul-fonate whose keryl group is an alkyl group derived from petroleum hydrocarbons and contains 11-16 carbon atoms, said sodium kerylbenzenesulfonate being present in its at least 35% active agent form; and 3-10% of an inhibitor compound selected from the group consisting of the zincates, berylliates and aluminates of sodium and the sulfates of zinc, beryllium and aluminum compounds and corresponding to a 0.85-5.66% Zn0 equivalent weight, a .009-1.41% BeO equivalent weight, and a 0.47-6.22% A1203 equivalent weight respectively.

10. A detergent composition inhibited against deteriorative action on vitreous and ceramic surfaces, consisting essentially of 23-25% by weight of a carbonate selected from the group consisting of sodium bicarbonate and modified soda, 15-22% of sodium tripolyphosphate, 49-55% of sodium kerylbenzenesulfonate Whose keryl group is an alkyl group derived from petroleum hydrocarbons and contains 11-16 carbon atoms, said sodium kerylbenzenesulfonate being in its 40-70% active agent form; and 4-6% of an inhibitor compound selected from the group consisting of the zinc ates, berylliates and aluminates of sodium and the sulfates of zinc, beryllium and aluminum compounds and corresponding to a l.13-3.40% Zn0 equivalent weight, a .012-0.84% BeO equivalent weight, and a 0.61-3.73% A1203 equivalent weight, respectively.

11. The detergent composition of the following formulation:

11 12. The detergent composition ofthe following formulation:

In at PerbCent gre ants Y Weight Sodium kerylbenzenesulfonate (40% active agent) 55 Sodium bicarbonate (NBHCOs) 25 Sodium tripolyphosphate (Na P O 15 NaHZnO-Hz0 reaction product (30% Z110 content).

13. The detergent composition of the following formulation:

. Per Cent Ingredient byWeight Sodium kerylbenzenesulfonate (40% active agent) 51 Sodium bicarbonate (NaHC 0;) 23 Sodium tripoiyphosphate (NasPaOm) 22 Aluminum sulfate (Ah(SO4);.14H;O)

Per Cent Ingredients by Weight Sodium kerylbenzenesuifonate (40% active agent) 49 Sodium bicarbonate (NaHCm) 23 Sodium tripolyphosphate (NaiP; 1o) 22 Zinc sulfate (ZnSO.7H2O) 6 12 16. The method of washing glassware and dishware, which comprises immersing suchware in a 0.3-1.0% by weight concentration aqueous solution of the detergent composition of the following formula:

- Per Cent Ingredients by Weight Sodium kerylbenzenesulfonate (40% active agent) 54 Sodium bicarbonate (N aH C 03) 23 Sodium tripolyphosphate (NasPaOm) i. 22 Aluminum sulfate (1112(800314112 0) 1 LESLIE R. BACON JOSEPH V; OTRHALEK. I

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,241,984 Cooper May 13, 1941 2,394,320 McGhie Feb. 5, 1946 2,419,805 Wegst Apr. 29, 1947 2,447,297 Wegst Aug. 17, 1948 

1. A DETERGENT COMPOSITION INHIBITED AGAINST DETERIORATIVE ACTION ON VITREOUS AND CERAMIC SURFACES, CONSISTING ESSENTIALLY OF 20-30% BY WEIGHT OF A CARBONATE SELECTED FROM THE GROUP CONSISTING OF SODIUM BICARBONATE, MODIFIED SODA AND SODIUM CARBONATE, 10-40% OF A PHOSPHATE SELECTED FROM THE GROUP CONSISTING OF SODIUM TRIPOLYPHOSPHATE, SODIUM TETRAPHOSPHATE AND SODIUM HEXAMETAPHOSPHATE, 40-70% OF A SYNTHETIC DETERGENT SELECTED FROM THE GROUP CONSISTING OF SODIUM ALCOHOL IN THE BATH BEING LOWER THAN THE PROSALTS OF ALKYL SULFONATES, ALKYL SULFATES AND ALKYL 10-18 CARBON ATOMS, SAID SYNTHETIC DETERGENT BEING PRESENT IN AT LEAST 35% ACTIVE AGENT FORM; AND 3-10% OF AN INHIBITOR COMPOUND SELECTED FROM THE GROUP CONSISTING OF ZINCATES, BERYLLIATES AND ALUMINATES OF SODIUM AND THE SULFATES OF ZINC, BERYLLIUM AND ALUMINUM COMPOUNDS AND CORRESPONDING TO A 0.85-5.66% ZNO EQUIVALENT WEIGHT, A .009-1,41% BEO EQUIVALENT WEIGHT, AND A 0.47-6.22% AL2O3 EQUIVALENT WEIGHT, RESPECTIVELY. 